methyl E-3-<1,2-bis(tert-butyldimethylsiloxy)-4-methoxycarbonylcyclopent-2-en-1-yl>propenoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl E-3-<1,2-bis(tert-butyldimethylsiloxy)-4-methoxycarbonylcyclopent-2-en-1-yl>propenoate
• 英文别名: methyl (1S,4R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-4-[(E)-3-methoxy-3-oxoprop-1-enyl]cyclopent-2-ene-1-carboxylate
• 化学式: C₂₃H₄₂O₆Si₂
• 分子量: 470.754
• InChiKey: LLFSWZIPJGVMJG-ZSOXJLGJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.57
• 重原子数：
  31
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  methyl (E)-4-(tert-butyldimethylsiloxy)-2,4-pentadienoate 在 pentacarbonyl(1-methoxybenzylidene)chromium(0) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 8.0h， 以99%的产率得到methyl E-3-<1,2-bis(tert-butyldimethylsiloxy)-4-methoxycarbonylcyclopent-2-en-1-yl>propenoate
  参考文献：
  名称：

  New Surprises with Fischer Carbene Complexes: Formal[3+2] Cycloadditions with and without Preeceding Carben–Ligand Matathesis

  摘要：

  DOI：

  10.1002/anie.199702831

文献信息

• Reactions of Fischer Carbene Complexes with Siloxydienes: Formation of Cycloheptadiene and Cyclopentene Derivatives—Formal [2+1] Cycloaddition Followed by Cope Rearrangement Versus Formal [3+2] Cycloaddition with or without Preceding Carbene-Ligand Metathesis
  作者：Matthias Hoffmann、Matthias Buchert、Hans-Ulrich Reißig

  DOI：10.1002/(sici)1521-3765(19990301)5:3<876::aid-chem876>3.0.co;2-t

  日期：1999.3.1

  Thermal reactions of the alpha,beta-unsaturated Fischer carbene complexes 3-5 with the siloxydienes 6 and 7 mainly furnished the expected cyclohepta-1,4-dienes such as 9, 10, 12, 14, and 15, whose formation is explained by a formal [2+1] cycloaddition followed by Cope rearrangement. The rather electron-rich carbene complex 5 also afforded the cyclopentene derivatives II and 16 as by-products, which are probably formed by two distinct mechanisms. Single diastereomers of the cyclopentene derivatives 17 and 18 were isolated as the exclusive products of the reactions of 3 and 4, respectively, with the donor/acceptor-substituted 1,3-diene 8. This process is interpreted as a metalla Diels-Alder reaction to form a chromacyclohexene intermediate 25, which subsequently undergoes fragmentation to give cyclopentene derivatives with the required constitution. Most surprisingly, the reactions of simple carbene complexes 1 or 2 with the siloxydienes 7 or 8 yielded cyclopentene derivatives 19 and 20 that do not contain the carbene ligand of the precursor complexes. Instead, the constitution of the isolated products can be accounted for by a formal diene dimerization with fragmentation of a methylene unit. Their formation can be interpreted by an unprecedented sequence of carbene-ligand metathesis followed by a metalla Diels-Alder reaction and reductive fragmentation. All these results illustrate the great importance of electronic fine-tuning in the precursors involved in reactions of Fischer carbene complexes with 1,S-dienes.
• New Surprises with Fischer Carbene Complexes: Formal[3+2] Cycloadditions with and without Preeceding Carben–Ligand Matathesis
  作者：Matthias Hoffmann、Hans-Ulrich Reissig、Matthias Buchert

  DOI：10.1002/anie.199702831

  日期：1997.2.14